Cementitious mixture for materials having “easy-to-clean” properties by modification of the unset material by means of fluorine-containing active ingredients

Abstract

The present invention relates to a hydraulically setting mixture comprising: a) 6% to 25% by weight of cement, b) 50% to 90% by weight of at least one aggregate, and c) 0.01% to 8% by weight of at least one fluoroorganyl-substituted silicon compound, and also to materials produced from this mixture, more particularly components, concrete articles or mouldings. The invention further relates to the use of a hydraulically setting mixture of the invention for producing materials, more particularly components, concrete articles or mouldings, for example as facing concrete, where the surface of the materials exhibits only relatively low soiling tendency (“easy-to-clean” property) even on abrasion.

The invention claimed is:  
     
       1. A hydraulically setting mixture comprising:
 a) 6 to 25% by weight of cement, 
 b) 50 to 90% by weight of at least one aggregate, and 
 c) 0.01 to 8% by weight of at least one fluoroorganyl-substituted silicon compound. 
 
     
     
       2. The mixture of  claim 1 , further comprising
 d) 0.01 to 2% by weight of a plasticizer, 
 e) 0.01 to 1% by weight of at least one further auxiliary, or 
 both d) and e). 
 
     
     
       3. The mixture of  claim 1 , wherein
 the cement is selected from the group consisting of a portland cement, a composite cement, a cement comprising a pozzolan, and a blast furnace cement. 
 
     
     
       4. The mixture of  claim 1 , wherein
 the aggregate is at least one selected from the group consisting of an agglomerate, a sand, a gravel, a crushed material, porphyry, quartz flour, ground limestone, ground rock, fly ashes, microsilica, and a siliceous additive. 
 
     
     
       5. The mixture of  claim 1 , wherein
 the fluoroorganyl-substituted silicon compound is at least one selected from the group consisting of a fluoroorganyl-substituted silane and a fluoroorganyl-substituted siloxane. 
 
     
     
       6. The mixture of  claim 1 , wherein the fluoroorganyl-substituted silicon compound is selected from the group consisting of
 (i) a compound derived from formulae I, II, III, IV and/or V, optionally having a crosslinking structural element which forms a chain, cyclic, crosslinked and/or three-dimensionally crosslinked structure, where at least one structure in idealized form corresponds to formula I,
   (HO)[(HO) 1-x (R 2 ) x Si(A)O] a [Si(B)(R 3 ) y (OH) 1-y O] b [Si(C)(R 5 ) u (OH) 1-u O] c [Si(D)(OH)O] d H·(HX) e   (I)
 
 
 where, in formula I, the structural element is derived from alkoxysilane of the formulae II, III, IV and/or V and 
 A corresponds to an aminoalkyl radical H 2 N(CH 2 ) f (NH) g (CH 2 ) h (NH) m (R 7 ) ) n — in the structural element derived from the general formula II,
   H 2 N(CH 2 ) f (NH) g (CH 2 ) h (NH) m (R 7 ) n Si(OR 1 ) 3-x (R 2 ) x   (II),
 
 
 where f is an integer of 0 to 6, where g=0 when f=0 and g=1 when f>0, h is an integer of 0 to 6, x=0 or 1, m=0 or 1 and n=0 or 1, where n+m=0 or 2 in formula II, and R 7  is a linear, branched or cyclic divalent alkyl group having from 1 to 16 carbon atoms 
 B corresponds to a fluoroalkyl radical R 4 —Y—(CH 2 ) k — in the structural element derived from the formula III,
   R 4 —Y—(CH 2 ) k Si(R 3 ) y (OR 1 ) 3-y   (III),
 
 
 where R 4  is a monofluorinated, oligofluorinated or perfluorinated alkyl group having from 1 to 9 carbon atoms or a monofluorinated, oligofluorinated or perfluorinated aryl group, Y is a CH 2 , O or S group, R 3  is a linear, branched or cyclic alkyl group having from 1 to 8 carbon atoms or an aryl group, k=0, 1 or 2 and y=0 or 1 in formula III and/or VI, 
 C corresponds to an alkyl radical R 5 — in the structural element derived from the formula IV,
   R 6 —Si(R 5 ) u (OR 1 ) 3-u   (IV),
 
 
 where R 5  is a linear or branched alkyl group having from 1 to 4 carbon atoms, 
 D is an alkyl radical R 6 — in the structural element derived from the formula IV,
   R 6 —Si(OR 1 ) 3   (V),
 
 
 where R 6  in the abovementioned formulae is a linear, branched or cyclic alkyl group having from 1 to 8 carbon atoms, and 
 the radicals R 1  in the formulae II, III, IV, V and/or VI are each, independently of one another, a linear, branched or cyclic alkyl group having from 1 to 8 carbon atoms or an aryl group; where R 2 , R 3  and/or R 5  in the abovementioned formulae each correspond, independently of one another, to a linear or branched alkyl radical having from 1 to 4 carbon atoms, and 
 in formula (I), HX is an acid, where X is an inorganic or organic acid radical, where x, y and u are each, independently of one another, 0 or 1 and a, b, c, d and e are each, independently of one another, integers where a≧0, b≧0, c≧0, d≧0, e≧0 and (a+b+c+d)≧2, 
 (ii) a compound in which the organosiloxanes are cocondensates or block cocondensates or mixtures of these derived from at least two of the abovementioned alkoxysilanes of the general formulae II, III, IV and V, 
 (iii) a monomeric fluoroorganyl-substituted silicon compound of the formula VI
   R 4 —Y—(CH 2 ) k Si(R 3 ) y (OR 1 ) 3-y   (VI),
 
 
 where R 4 , Y, R 1 , R 3 , k and y are as defined above, and 
 a mixture of a plurality of monomeric compounds of the formula VI. 
 
     
     
       7. The mixture of  claim 1 , wherein
 the fluoroorganyl--substituted silicon compound is present as a liquid monomeric compound or in solution or as an aqueous dispersion or emulsion or as a paste or cream preparation. 
 
     
     
       8. The mixture of  claim 1 , further comprising 1 to 20% by weight of water. 
     
     
       9. A process for producing a mixture, comprising admixing the mixture of  claim 1  with water in a mixing apparatus. 
     
     
       10. A material comprising the mixture of  claim 1 . 
     
     
       11. A facing concrete comprising the mixture of  claim 1 . 
     
     
       12. A process of modifying a hydraulically setting mixture, comprising contacting the mixture with a fluoroorganyl-substituted silicon compound, thereby obtaining the mixture of  claim 1 . 
     
     
       13. A component, concrete product or molding comprising the mixture of  claim 1 . 
     
     
       14. The mixture of  claim 1 , wherein the aggregate comprises an agglomerate having a maximum particle size of 32 mm. 
     
     
       15. The mixture of  claim 1 , wherein the aggregate comprises a sand having a maximum particle size of 5 mm. 
     
     
       16. The mixture of  claim 1 , wherein the fluoroorganyl-substituted silicon compound comprises a monomeric fluoroalkyl-substituted silane. 
     
     
       17. The mixture of  claim 1 , wherein the fluoroorganyl-substituted silicon compound comprises a monomeric fluoroalkyl-substituted siloxane. 
     
     
       18. The mixture of  claim 1 , comprising:
 a) 10 to 20% by weight of cement, 
 b) 65 to 85% by weight of the at least one aggregate, and 
 c) 0.02 to 5% by weight of the at least one fluoroorganyl-substituted silicon compound. 
 
     
     
       19. The mixture of  claim 1 , comprising:
 a) 12 to 18% by weight of cement, 
 b) 70 to 80% by weight of the at least one aggregate, and 
 c) 0.05 to 2% by weight of the at least one fluoroorganyl-substituted silicon compound. 
 
     
     
       20. The mixture of  claim 2 , comprising:
 d) 0.05 to 0.5% by weight of a plasticizer, 
 e) 0.01 to 1% by weight of at least one further auxiliary, or 
 both d) and e). 
 
     
     
       21. The mixture of  claim 6 , wherein the fluoroorganyl-substituted silicon compound is a compound of formula VI or a mixture of a plurality of compounds of formula VI. 
     
     
       22. The mixture of  claim 6 , wherein the fluoroorganyl-substituted silicon compound is a compound derived from a compound of formula I, optionally having a crosslinking structural element forming a chain, cyclic, crosslinked, and/or three-dimensionally crosslinked structure.